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WO2000061676A1 - Composite de resine polyolefinique, composite de resine thermoplastique et procede de production du composite de resine thermoplastique - Google Patents

Composite de resine polyolefinique, composite de resine thermoplastique et procede de production du composite de resine thermoplastique Download PDF

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Publication number
WO2000061676A1
WO2000061676A1 PCT/JP2000/002337 JP0002337W WO0061676A1 WO 2000061676 A1 WO2000061676 A1 WO 2000061676A1 JP 0002337 W JP0002337 W JP 0002337W WO 0061676 A1 WO0061676 A1 WO 0061676A1
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WO
WIPO (PCT)
Prior art keywords
layered silicate
group
composite material
resin composite
polyolefin
Prior art date
Application number
PCT/JP2000/002337
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English (en)
Japanese (ja)
Inventor
Koichiro Iwasa
Naoki Ueda
Koichi Shibayama
Juichi Fukatani
Original Assignee
Sekisui Chemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP11203109A external-priority patent/JP2001026724A/ja
Priority claimed from JP11238433A external-priority patent/JP2000355640A/ja
Priority claimed from JP24380099A external-priority patent/JP2001064454A/ja
Application filed by Sekisui Chemical Co., Ltd. filed Critical Sekisui Chemical Co., Ltd.
Priority to EP00915473A priority Critical patent/EP1193290A4/fr
Publication of WO2000061676A1 publication Critical patent/WO2000061676A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/008—Additives improving gas barrier properties

Definitions

  • thermoplastic resin composite material Description Polyolefin resin composite material, thermoplastic resin composite material, and method for producing thermoplastic resin composite material Field of the Invention
  • the present invention relates to a polyolefin-based resin composite material or a thermoplastic resin composite material called a nanocomposite, and more particularly, to a polyolefin resin containing a polyolefin-based resin or a thermoplastic resin resin and an organically modified layered silicate.
  • the present invention relates to a fin-based resin composite material, a thermoplastic resin composite material, and a method for producing the thermoplastic resin composite material.
  • Layered silicate has a thickness of about 1 nm and an average aspect ratio (ratio of length or width to thickness) of about 20 to 200.
  • a composite material in which flaky silicate crystals of a layered silicate are dispersed in such a polymer is called a nanocomposite.
  • the distance between the layers is increased in advance by printing the amino carboxylic acid into the layered silicate with a single force. Then, by introducing the polyamide monomer, p-protatatam, between layers and simultaneously performing polycondensation, it is possible to form a structure in which lamellar silicate flakes are uniformly dispersed in the polyamide resin. Has been described. However, it is generally very difficult to uniformly disperse a layered silicate that is inherently highly hydrophilic in not only hydrophilic polymers such as polyamides, but also polymers such as polyethylene and polypropylene, which are non-polar polymers. Various approaches have been disclosed to solve this problem.
  • Japanese Patent Application Laid-Open No. 9-189390 discloses that a layered silicate is polymerized by mixing an organic dispersion obtained by swelling and dispersing an organized layered silicate with a solvent and a vinyl polymer compound in a molten state. Dispersion methods are disclosed therein.
  • Japanese Patent Application Laid-Open No. H10-182828 discloses that an organically modified layered silicate and a hydrogen bonding functional group of 0.001 mmo 1 / g or more and 0.45 mmo 1 / g are used.
  • a polyolefin-based resin composite material in which the layered silicate swells infinitely in the polymer can be prepared by melt-kneading the polyolefin oligomer and the polyolefin polymer contained therein.
  • the method described in Japanese Patent Application Laid-Open No. 9-189390 requires the use of a solvent, and requires complicated steps such as a polymer dissolving step, an organically modified layered silicate swelling step, and a solvent removing step. Since it involves processes, it is not always practical from an industrial point of view. According to the inventors of the present application, in the method described in Japanese Patent Application Laid-Open No.
  • a material in which crystal flakes of a layered silicate are uniformly dispersed in a polymer is used as an industrial material. It turned out to be extremely difficult to use. That is, since the functional groups in the oligomer react with the hydroxyl groups on the surface of the layered silicate during the melt-kneading, the hydroxyl groups of the layered silicate are not necessarily efficiently treated by the functional group. For this reason, a large amount of oligomer is required in order to actually achieve uniform dispersion of the layered silicate. Such an oligomer component is contained in a large amount in the polymer This is not preferable in terms of physical properties and cost.
  • Japanese Patent Application Laid-Open No. 8-32025 discloses a process of contacting an organic cation with a layered compound and a process of swelling the contacted layered compound with an organic solvent (particularly, an aromatic solvent). And a step of kneading the swollen layered compound with the elastomer, and discloses a method for producing an elastomer containing an inorganic filler.
  • Japanese Patent Application Laid-Open No. Hei 9-148856 describes that a layered silicate is polymerized by mixing an organic dispersion obtained by swelling and dispersing an organically modified layered silicate with a solvent and a vinyl polymer compound in a molten state. Dispersion methods are disclosed therein.
  • the so-called nanocomposite obtained by finely dispersing the layered silicate is applied to hard materials that do not basically contain a plasticizer, such as polyamide and polyolefin, but contains a plasticizer. No known nanocomposite of a soft composition was found.
  • a main object of the present invention is to provide a polyolefin-based resin composite material in which lamellar silicate flakes are uniformly dispersed in a polyolefin-based polymer, whereby the mechanical strength, thermal properties and gas barrier properties are improved. To do so.
  • Another object of the present invention is to provide a thermoplastic resin composite material in which lamellar silicate flakes are uniformly dispersed in a thermoplastic resin, thereby improving mechanical strength, thermal properties and gas barrier properties. The purpose is to provide a manufacturing method thereof.
  • the polyolefin-based resin composite material and the thermoplastic resin composite material provided by the present invention are nanocomposites composed of a layered silicate, and the flaky crystals of the layered silicate are expanded. Resin has entered the.
  • the nanocomposite preferably has an aspect ratio of 20 or more, more preferably 20 to 500, and still more preferably 50 to 200.
  • the “average particle size” of the layered silicate described later is an average value of the values represented by (major axis + minor axis) Z 2.
  • a polyolefin-based resin composite material containing 100 parts by weight of a polyolefin-based resin and 0.1 to 50 parts by weight of an organically modified layered silicate
  • the silicate is an organically modified layered silicate in which a metal ion contained as an exchangeable cation in the crystal structure has been ion-exchanged with a cationic surfactant, and a hydroxyl group on the side surface of the crystal of the organically modified layered silicate
  • the polyolefin-based resin composite material is chemically modified with a chemical substance having a functional group having a chemical bond or a chemical affinity with a hydroxyl group at a molecular terminal.
  • the functional group having a chemical bond or a chemical affinity with the hydroxyl group is an alkoxy group, an alkoxysilyl group, an epoxy group, a carboxyl group, a hydroxyl group, a maleic anhydride group, It is one selected from the group consisting of an isocyanate group and an aldehyde group.
  • the chemical substance has two or more carbon atoms.
  • the chemical substance contains at least one reactive functional group in addition to a functional group having a chemical bond or a chemical affinity with a hydroxyl group at a molecular terminal. .
  • the reactive functional group is at least one selected from the group consisting of a vinyl group, an amino group, an epoxy group, and an acryloyl group.
  • the chemical substance contains a straight chain containing 12 or more carbon atoms.
  • the average interlayer distance of the layered silicate detected by X-ray diffraction measurement is 6 nm or more.
  • the number of layered silicate particles having an average particle diameter of 1 ⁇ m or more is 100 or less in a range of 100 / m square.
  • the average interlayer distance of the layered silicate constituting the polyolefin-based resin composite material of the first invention and the second invention described below is detected by X-ray diffraction measurement.
  • the average interlayer distance is 6 nm or more. Preferably, there is.
  • the layers of the layered silicate that are not dispersed cohere to each other due to the ionic bonding force, and exist stably at an interlayer distance of about 1 nm.
  • the ionic interaction between the layers that is, by reducing the interlayer distance to 6 nm or more, it becomes possible to crush the layered silicate flakes and disperse them in the resin.
  • the mechanical strength and the thermal properties of the composite can be significantly improved.
  • a polyolefin-based resin composite material containing 100 parts by weight of a polyolefin resin and 0.1 to 50 parts by weight of an organically modified layered silicate, Silicates exchange during the crystal structure Organic phyllosilicate in which the metal ion contained as a cationic cation is ion-exchanged with a cationic surfactant, and the crystal side surface of the organic phyllosilicate is a compound having anionic surfactant activity.
  • a polyolefin-based resin composite material characterized by being chemically modified is provided.
  • the compound having an anionic surfactant activity is selected from the group consisting of a carboxylate, a sulfonate, a sulfate, a phosphate, and a polyphosphate. It is at least one type of surfactant.
  • the compound having an anionic surfactant activity contains at least one reactive functional group other than the anionic site in its molecular chain.
  • the reactive functional group is at least one selected from the group consisting of a vinyl group, an amino group, an atalyloyl group, and an epoxy group.
  • the compound having an anionic surfactant activity has a long chain containing 12 or more carbon atoms.
  • the average interlayer distance of the layered silicate detected by X-ray diffraction measurement is 6 nm or more.
  • the number of layered silicate particles having an average particle diameter of 1 ⁇ m or more is 100 or less in a range of 100 ⁇ m square.
  • a thermoplastic resin contains a thermoplastic resin, a layered silicate, and a plasticizer, and the layered silicate is finely dispersed. A composite material is provided.
  • 0.1 to 100 parts by weight of the above-mentioned layered silicate and 2 to 300 parts by weight of a plasticizer are mixed with 100 parts by weight of the thermoplastic resin.
  • an organically modified layered silicate is used as the layered silicate.
  • thermoplastic resin a polybutyral resin is used as the thermoplastic resin.
  • the average interlayer distance of the layered silicate detected by X-ray diffraction measurement is 6 nm or more.
  • the number of layered silicate particles having an average particle size of 1 ⁇ m or more in 100 ⁇ m square is 100 or less.
  • the average interlayer distance of the layered silicate constituting the thermoplastic resin composite material of the third invention is detected by X-ray diffraction measurement, and the average interlayer distance is preferably 6 nm or more.
  • the mechanical strength and the thermal properties of the composite can be significantly improved.
  • the fourth invention of the present application is a method for producing a thermoplastic resin composite material according to the third invention, wherein a step of mixing a layered silicate and a plasticizer to obtain a mixture, the mixture and the thermoplastic resin And mixing the two.
  • an organically modified layered silicate is used as the layered silicate.
  • thermoplastic resin 0.1 to 100 parts by weight of a layered silicate and 2 to 300 parts by weight of a plasticizer are blended with 100 parts by weight of the thermoplastic resin.
  • the polyolefin resin in the first and second inventions is not particularly limited, but may be propylene homopolymer, random and block copolymer of propylene and ethylene, ethylene homopolymer, and ethylene. And ⁇ -olefin, a homopolymer of polybutene, and a homopolymer of polyisoprene.
  • hyolephine examples include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-pentene, 1-octene and the like. Further, these polyolefins may be appropriately combined in consideration of physical properties to be obtained.
  • Additives may be appropriately added to the polyolefin resin used in the first and second inventions. Additives such as antioxidants, light stabilizers, ultraviolet absorbers, lubricants, flame retardants, antistatic agents and the like are appropriately used to obtain desired physical properties. It is also possible to add a small amount of a crystal nucleating agent to help refine the crystal and to make the properties uniform.
  • Layered silicate refers to a silicate mineral having exchangeable cations between layers.
  • the type of phyllosilicate is not particularly limited.
  • smectite-based clay minerals there are also permikilite, halloysite, etc.
  • a synthesized product can be preferably used. More preferably, it is desirable to use a swelling my force having a large shape anisotropy effect defined by the formula (1) in terms of mechanical strength and gas barrier properties of the composite material.
  • Shape anisotropy effect crystal side surface (A) area Z layered crystal surface (B) area
  • Equation (1) Note that the crystal side surface (A) is the side surface of the flaky crystal as schematically shown in FIG. 1, and the flaky crystal faces the crystal surface (B). Check the side that is.
  • the layered silicate used in the present invention preferably has an average length of 0.01 to 3 ⁇ , a thickness of 0.00:! To l Atm, and an aspect ratio of 20 to 500. More preferably, the average length is 0.05 to 2 / xm, and the thickness is 0.0 :! 0.5 ⁇ m, aspect ratio 50-200.
  • the cation exchange capacity of the layered silicate used in the present invention is not particularly limited, but is preferably from 50 to 200 milliequivalents (100 g). If the equivalent of less than 50 milligrams is less than 100 g, the amount of cationic surfactant that is intercalated between the crystal layers by ion exchange is small, and the layers may not be sufficiently depolarized. . On the other hand, if it exceeds 200 milliequivalents / 10 Og, the bonding force between the layers of the layered silicate becomes strong, and it may be difficult to delaminate the crystal flakes.
  • the term “organized layered silicate” refers to a layered silicate in which a cation, that is, a metal ion, is ion-exchanged with a cationic surfactant.
  • the cationic surfactant is not particularly limited. Quaternary ammonium salts, quaternary phosphonium salts, and the like, preferably charcoal A quaternary ammonium salt having an alkyl chain with a prime number of 8 or more is used. When the alkyl chain having no more than 8 carbon atoms is not contained, the hydrophilicity of the alkyl ammonium ion is so strong that the interlayer of the layered silicate cannot be sufficiently depolarized.
  • quaternary ammonium salts include, for example, lauryltrimethylammonium salt, stearyltrimethylammonium salt, trioctylammonium salt, distearyldimethylammonium salt, di-hardened tallow dimethylammonium salt, distearyldibenzylammonium salt. And the like.
  • the polyolefin-based resin composite material of the first and second inventions is composed of 0.1 to 50 parts by weight of the polyolefin-based resin and 0.1 to 50 parts by weight of the organically modified layered silicate.
  • the “functional group having a chemical bond or a chemical affinity with a hydroxyl group” is not particularly limited, but it needs to be a functional group having at least a chemical affinity with a hydroxyl group, and may be an alkoxy group, an alkoxysilyl group, or an epoxy group.
  • a carboxyl group, a hydroxyl group, a maleic anhydride group, an isocyanate group, an aldehyde group and the like are preferably used.
  • Examples of such a chemical substance include a silane compound containing the functional group, a titanate compound, a glycidyl compound, a carboxylic acid, and an alcohol.
  • a chemical substance having an alkoxysilyl group is used.
  • silane compound containing an alkoxysilyl group for example, silane
  • a silane coupling agent having an alkoxysilyl group can be represented by the general formula (2).
  • examples of R 1 include methyl, ethyl, propyl, isopyryl, hexyl, octadecyl, and an alkyl group containing at least 12 carbon atoms.
  • the chemical comprises a long chain having at least 12 carbon atoms. This is due to the following reasons.
  • R 1 may contain a reactive functional group at the molecular terminal of the chemical substance in addition to a functional group having a chemical bond or a chemical affinity with a hydroxyl group.
  • Examples of the reactive functional group include an aminopropyl group, N— / 3 (aminoethyl) ⁇ -aminopropyl group, a vinyl group, an epoxy group, an acryloyl group, a maleic anhydride group, an alkoxy group, a carboxyl group, and a hydroxyl group.
  • the reason for using these reactive functional groups is as follows. By reacting these reactive functional groups with a polyolefin-based resin as appropriate, the reactive functional groups can act as physicochemically active sites that generate delamineate.
  • a graft reaction with a polyolefin resin can be performed by using a radical generator or a peroxide having an appropriate half-life temperature during kneading. It becomes.
  • R1 (or increase the molecular weight). This further enhances the effect of the entanglement of the molecular chains, and makes it possible for each flake of the layered silicate to be easily peeled off.
  • the reagent to be reacted with the reactive functional group is not particularly limited.
  • the fact that it is directly reacted with the polyolefin resin used as the matrix resin is also effective for obvious reasons as described above.
  • the reactive functional group is more preferably a vinyl group, an amino group, an epoxy group, or an acryloyl group among the above groups.
  • a vinyl group is used as the reactive functional group, a chemical bond can be easily formed between the reagent and the alkyl group having a vinyl group by a trigger such as heat, a radical initiator, ultraviolet rays, or an electron beam.
  • a trigger such as heat, a radical initiator, ultraviolet rays, or an electron beam.
  • a heat, an acid, a base, or the like can be used to easily trigger a reaction between an isocyanate group, a maleic anhydride group, a carboxyl group, and a carbonyl group.
  • a chemical bond can be formed.
  • a chemical bond can be easily formed between a reagent having a hydroxyl group and the like by a trigger such as heat, an acid, or a base.
  • a trigger such as heat, an acid, or a base.
  • a chemical bond can be easily formed by a physical trigger such as an electron beam, light, or ultraviolet light, or a chemical trigger such as an azo compound or a peroxide.
  • R 2 When any one of R 2, R 3, and R 4 does not have a functional group having a chemical bond or a chemical affinity with a hydroxyl group, the structure is not particularly limited, but a methyl group, an ethyl group Groups, methoxy groups, ethoxy groups and the like.
  • the chemical substance preferably has two or more carbon atoms, and examples thereof include a silane coupling agent represented by the general formula (2), such as vinyltrimethoxysilane, vinyltriethoxysilane, or the like.
  • a silane coupling agent represented by the general formula (2), such as vinyltrimethoxysilane, vinyltriethoxysilane, or the like.
  • the most remarkable point in the present invention is that the hydroxyl group on the crystal side surface of the organically modified layered silicate is converted into a functional group having chemical bonding or chemical affinity with the hydroxyl group. Is to efficiently perform chemical modification with a chemical group having a compound at the terminal of the molecule. This makes it possible to efficiently treat the hydroxyl groups on the crystallized surface of the organically modified layered silicate with a small amount of a chemical substance. Furthermore, since the chemical composition is bonded to the end face of the layered silicate crystal, it can be expected that the chemical composition acts as a physicochemical active point in delaminating each crystal flake. .
  • the operation and effect of the present invention will be described in detail.
  • crystal flakes of layered silicate 1 schematically shown in FIG. 1 are tetrahedral 11 in which four oxygen ions are coordinated around ions such as silicon, for example, montmorillonite shown in FIG. It is composed of an octahedron 12 in which six oxygen ions or hydroxyl ions are coordinated around ions such as aluminum.
  • Each crystal flake has ions such as sodium and calcium arranged on the layered crystal surface (B). Thus, they are linked by ionic bonding force.
  • the layered silicate can be ion-exchanged with a cationic surfactant such as sodium ammonium ion or calcium ion between the layers.
  • a cationic surfactant such as sodium ammonium ion or calcium ion between the layers.
  • a highly non-polar cation species such as distearyl dimethyl ammonium salt as the alkyl ammonium salt, the surface of the layered crystal (B) is depolarized and the layered silicate in the non-polar polymer is used. Is relatively improved.
  • the hydroxyl groups present on the side surface (A) of the crystal remain as polar sites even after the above ion exchange, which is one of the reasons why the organically modified layered silicate cannot be uniformly dispersed in the non-polar polymer.
  • the hydroxyl group present on the crystal side face (A) is chemically modified with a chemical substance having a functional group having chemical bonding or chemical affinity with the hydroxyl group at the terminal of the molecule.
  • the compatibility between the polyolefin resin, which is a polar polymer, and the phyllosilicate is significantly improved, and the phyllosilicate can be easily and uniformly dispersed in the polymer.
  • the chemical substance has two or more carbon atoms, the compatibility with the polyolefin resin, which is a nonpolar polymer, is further improved.
  • the more the crystalline flakes of the layered silicate are dispersed in the polymer the more the elastic modulus of the composite material of the polyolefin resin and the layered silicate is remarkably improved.
  • This phenomenon can be explained by the fact that the area of the interface between the layered silicate and the resin increases as the dispersion of the crystal flakes increases. That is, the molecular motion of the polymer is restricted at the bonding surface between the polymer and the inorganic crystal.
  • the mechanical strength such as the elastic modulus of the polymer increases, so that the polymer strength can be increased more efficiently as the dispersion ratio of the crystal flakes increases.
  • the finer the crystalline flakes of the layered silicate are dispersed in the polymer the more significantly the gas barrier properties of the polyolefin-based resin composite material are significantly improved. Since gas molecules are much easier to diffuse in polymers than in inorganic materials, when gas molecules diffuse in the composite material of the present invention, the polyolefin is bypassed while bypassing the layered silicate 1 as shown in FIG. Diffuses in system resin 2. Therefore, also in this case, the gas barrier can be efficiently increased as the dispersion ratio of the crystal flakes increases.
  • the dispersion ratio of crystal flakes can be remarkably improved, and as a result, a polyolefin material having excellent mechanical strength and gas barrier properties can be obtained.
  • the method described in Japanese Patent Application Laid-Open No. 9-189390 discloses a method of impregnating an organic solvent between layers of a layered silicate in advance to increase the distance between layers, thereby improving the dispersibility of crystal flakes.
  • the aim was to increase it, in fact, although the oxygen barrier property was improved, the flexural modulus was hardly improved, probably because the residual solvent could not be easily removed. It is difficult to completely remove the solvent with the ventro of an extruder, and in that sense, adoption from an industrial point of view is considered to be a difficult method.
  • Compound having anionic surfactant activity used in the second invention Is not particularly limited, but must be a functional group having high chemical affinity with a positive charge.
  • Examples of compounds containing these functional groups include carboxylic acid salts such as sodium perfluorophosphate, sodium stearate, sodium oleate, etc., and sodium lauryl alcohol sulfate, lauryl alcohol sulfate containing anionic functional groups.
  • the compound having the anionic surface activity preferably contains one or two or more reactive functional groups other than the anionic portion in the molecular chain. Further, it is preferable that the compound having anionic surface activity has a straight chain containing at least 12 carbon atoms.
  • the molecular chain of the compound chemically modified on the crystal side surface (A) is entangled with the molecular chain of the resin when kneading with the polyolefin resin, thereby forming a crystal flake.
  • the reactive functional group is not particularly limited, and examples thereof include a vinyl group, an atalyloyl group, an epoxy group, a maleic anhydride group, an alkoxy group, a carboxyl group, and a hydroxyl group.
  • a vinyl group and an acryloyl group are preferable from the viewpoint of easy synthesis of the surfactant.
  • the most remarkable point in the second invention is that the crystal side surface (A) of the organically modified layered silicate is chemically modified with a compound having anionic surface activity. Accordingly, it is expected that the compound having anionic surface activity can act as a physicochemical active point when delaminating each crystal flake of the organically modified layered silicate.
  • the positive charge existing on the crystal side surface (A) in FIG. 2 remains after ion exchange, and this indicates that the organically modified layered silicate is nonpolar.
  • uniformly c second invention was one of the reasons which can not be dispersed in the polymer, the positive charge of the crystal side (a), the Furudo chemically modifying at the agents having Anion of surfactant activity Because of this feature, the compatibility between the polyolefin resin, which is a nonpolar polymer, and the layered silicate is significantly improved, and the layered silicate can be easily and uniformly dispersed in the polymer.
  • the compound is much smaller than on the crystal surface (B). This can be easily explained by the model shown in Fig.3. In other words, assuming that the adhesive sheet is to be peeled off from the substrate to be adhered, it is much smaller to peel off the sheet by the edge of the sheet than by peeling the sheet near the center of the sheet. Can be peeled off. According to this mechanism, it can be easily inferred that by reacting the chemical composition with the polyolefin-based resin, the stress for delamination generated during kneading can be further improved.
  • the publication of Japanese Patent Application Laid-Open No. 10-182882 does not take such points into consideration, and therefore it is difficult to achieve uniform dispersion. It was revealed.
  • thermoplastic resin used in the third and fourth inventions is not particularly limited, but may be polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, polystyrene, polyolefin, polymethacrylic acid ester, polyacrylinoleic acid.
  • Use resins such as esters, polyvinyl alcohol, cellulose esters, and nitrocellulose, NBR, SBR, black rubber, isoprene rubber, butadiene rubber, butynole rubber, urethane rubber, and various rubbers such as norbornene rubber. be able to.
  • polystyrene resin examples include propylene homopolymer, propylene and ethylene random and block copolymers, ethylene homopolymer, ethylene and hyolefin copolymer, polybutene homopolymer, polyisoprene homopolymer and the like. Is mentioned.
  • ⁇ -olefin examples include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-peptene, 1-octene and the like.
  • thermoplastic resin Polyvinyl acetal resin obtained by acetalization with an aldehyde having 1 to 10 carbon atoms out of the moon is preferably used. I like it.
  • these resins may be blended in an appropriate combination in consideration of necessary physical properties.
  • the molecular weight and molecular weight distribution of the thermoplastic resin used in the third and fourth inventions are not particularly limited, but the weight average molecular weight force S 5,000 to 5,000 to 5,000 from the moldability and physical properties. It is preferable that the molecular weight distribution be 0 0, 0 0 0, preferably 20 0 0 0 to 1, 0 0 0, 0 0, and the molecular weight distribution be 2 to 80, preferably 3 to 40. .
  • the molecular weight distribution is expressed as weight average molecular weight / number average molecular weight.
  • the layered silicate may be used as it is or an organically treated layered silicate that has been treated in advance may be used, but it is more preferable to use an organically modified layered silicate.
  • the addition amount of the layered silicate or the organically modified layered silicate is preferably from 0.1 to 100 parts by weight based on 100 parts by weight of the thermoplastic resin. If the amount is less than 0.1 part by weight, the added amount is small and the desired physical properties cannot be sufficiently exhibited. If added in excess of 100 parts by weight, the resin content in the composite material is reduced, and physical properties such as impact resistance may be reduced, which is not desirable.
  • a more preferred addition amount of the layered silicate or the organized layered silicate is 1 to 20 parts by weight.
  • the phyllosilicate or organically phyllosilicate must be finely dispersed.
  • the amount of the layered silicate or the organically modified layered silicate having a particle size of ⁇ or more is preferably 100 or less, more preferably 50 or less per 100 / zm ⁇ 100 im.
  • plasticizer used in the present invention examples include, but are not particularly limited to, phosphate esters, phthalate esters, fatty acid ester types, glycol ester types, and epoxy types. Examples include tricresyl phosphate, trioctyl phosphate, dibutinolephthalate, dioctyl phthalate, dioctyl adipate, diotatinolease, dioctinoreserbate. And triethylene glycol-ethylbutylate, triethyleneglycol-ethylethylhexoate, triethyleneglycol-diptylsebacate, epoxidized soybean oil and the like. These plasticizers are properly used depending on the type of the thermoplastic resin in consideration of compatibility with the resin and the like.
  • the addition amount of the plasticizer is preferably 2 to 300 parts by weight based on 100 parts by weight of the thermoplastic resin. If the amount is less than 2 parts by weight, the phyllosilicate or the organized phyllosilicate is not sufficiently dispersed. Also, if the plasticizer is added in excess of 300 parts by weight, bleeding out of the plasticizer occurs, which is not preferable. A more preferable addition amount of the plasticizer is 5 to 100 parts by weight. The amount of the plasticizer is preferably 0.5 to 100 parts with respect to 1 part of the layered silicate or the organically modified layered silicate.
  • the amount of the plasticizer is preferably 5 to 100 parts by weight, and more preferably 30 to 70 parts by weight. .
  • thermoplastic resin composite material of the third invention is not particularly limited.
  • a layered silicate or an organically modified layered silicate and a plasticizer are mixed in advance to form a layered silicate. It is particularly preferable to add a salt or an organically modified layered silicate having sufficient interlayer spacing to a resin and to knead the mixture. In this case, a part of the plasticizer and the entire amount of the layered silicate or the organically modified layered silicate may be mixed, and then the remaining amount of the plasticizer may be added and mixed.
  • thermoplastic resin composite material used in the present invention may optionally contain additives such as an antioxidant, a light stabilizer, an ultraviolet absorber, a lubricant, a flame retardant, an antistatic agent, and the like.
  • the apparatus for mixing the plasticizer and the layered silicate or the organic layered silicate is not particularly limited, but a planetary stirrer, a wet mechanochemical apparatus, a Henschel mixer, a homogenizer, an ultrasonic irradiator and the like are generally used.
  • the equipment used for kneading the resin, plasticizer, layered silicate or organic layered silicate is not limited, but an extruder, a plastograph, a kneader, a Banbury mixer, a force render roll, etc. are used. be able to. In particular, from the viewpoint of continuous production, it is preferable to use an extruder.
  • thermoplastic resin composite material of the third invention can be used in various applications by various resins.
  • a composite material composed of a combination of polybutyral, a layered silicate or an organically modified layered silicate, and a plasticizer is suitably used for an interlayer for laminated glass, particularly for a multilayer interlayer.
  • an intermediate layer of an interlayer it can be used as an interlayer for laminated glass such as for buildings and automobiles.
  • composite materials consisting of a combination of polyvinyl chloride, a layered silicate or an organically modified layered silicate, and a plasticizer are used as soft vinyl chloride and rubber as agricultural bullet sheets and food packaging. It can be used for various purposes such as materials, leather, films, vibration damping sheets, wallpapers, tubes, paints, adhesives, etc.
  • the finer the layered silicate is dispersed in the resin the more the mechanical strength, gas barrier properties and transparency of the thermoplastic resin layered silicate composite are significantly improved.
  • the interfacial area between the layered silicate and the resin increases as the dispersion of the layered silicate increases. That is, since the molecular motion of the polymer is restricted at the interface between the resin and the inorganic crystal, the mechanical strength such as the elastic modulus of the polymer is increased. Polymer strength can be increased.
  • gas molecules are much easier to diffuse in the resin layer than in an inorganic material, when gas molecules diffuse in a composite material, they diffuse while bypassing inorganic substances. Therefore, the gas barrier property can be more efficiently improved as the degree of dispersion of the layered silicate increases.
  • a layered silicate when added to a transparent resin, if the size of the dispersed layered silicate is large, the light is scattered and becomes opaque. As scattering is reduced, light is more easily transmitted and transparency is improved.
  • FIG. 1 is a schematic perspective view of a layered silicate used to obtain a polyolefin-based resin composite material according to the present invention.
  • FIG. 2 is a partially enlarged conceptual diagram of the main part of the layered silicate shown in FIG.
  • FIG. 3 is a side view showing a state where the adhesive sheet is peeled off from the substrate.
  • FIG. 4 is a schematic cross-sectional view for explaining a state in which gas molecules permeate the polyolefin-based resin composite material according to the present invention. Description of the preferred embodiment
  • the following minerals were used as the layered silicate.
  • the following materials were used as the layered silicate containing a cationic surfactant.
  • compositions were used as chemical compositions for modifying the crystal side surface (A).
  • Aminoprobilt rimethoxysilane Shin-Etsu Chemical reagent
  • compositions were used as the polyolefin resin.
  • peroxides were used for the purpose of causing a graft reaction of unsaturated bonds contained in metaloxyl-trimethoxysilane or vinyltrimethoxysilane with a polypropylene resin.
  • Aminoprovir trimethoxysilane (Shin-Etsu Chemical reagent) Treated layer
  • the following compounds were used as reagents for causing a chemical reaction with the silicate.
  • compositions were used as resin oligomers used for comparison with the conventional technology.
  • the following organic solvents were used as solvents for comparison with the prior art. It is used for the purpose of impregnating between the layers of the organic slurry and extending the distance between the layers.
  • the treated powders A to F and the untreated powder were prepared by the following methods.
  • Processed powder A While stirring 500 g of DSDM-modified montmorillonite in a Henschel mixer, 100 g of a 2 wt% aqueous solution of aminoproxytrimethoxysilane was added dropwise over 3 minutes. After completion of the dropwise addition, stirring was further performed for 10 minutes. The treated powder was held in a vacuum drier whose temperature was controlled at 70 ° C., and dried for 8 hours to obtain treated powder A.
  • Treated powder B was prepared using octadecyltrimethoxysilane instead of aminopropyltrimethoxysilane in the method of preparing treated powder A above.
  • Processed powder C Among the methods for preparing the above processed powder A, methacryloxytrimethoxysilane was used instead of aminobutyral prilltrimethoxysilane. Processed powder c was prepared.
  • Treated powder C-2 Treated powder C-12 was prepared by using vinyltrimethoxysilane instead of aminopropyltrimethoxysilane in the method of preparing treated powder A above.
  • Treated powder C-3 Treated powder C-13 was prepared by using dalicidoxypropyltrimethoxysilane instead of aminopropyltrimethoxysilane in the preparation method of treated powder A above.
  • Treated Powder C-4 Among the methods for preparing the treated powder A, treated powder C-14 was prepared by using alkoxyxylyl polyisobutylene at both ends instead of aminopropyl trimethoxysilane.
  • Treated powder D was prepared by using the organic swelling my force instead of the DSDM-modified montmorillonite in the method of preparing the treated powder A.
  • Treated powder E was prepared by using a montmorillon mouth instead of the DSM-modified montmorillonite in the method of preparing the treated powder A.
  • Processed powder F was prepared by using montmorillonite in place of DSDM-modified montmorillonite and octadecyltrimethoxysilane in place of aminopropyltrimethoxysilane in the preparation method of process powder A above. .
  • the resin and each of the above powders are fed into a small extruder (TEX30) manufactured by Nippon Steel Works at a weight ratio of 92.7 / 7.7, and melted at a set temperature of 20 o ° c.
  • the kneaded and extruded strands were pelletized with a pelletizer.
  • the obtained pellets were thickened by a hot press adjusted to 200 ° C. A plate having a thickness of 2 mm or a thickness of 100 / im was formed.
  • the input material was liquid, it was injected at a predetermined mixing ratio from the middle of the extruder using a plunger pump or a gear pump.
  • a plunger pump was used for charging the liquid peroxide (Perhexa 25B) shown in Comparative Example 3 below.
  • the untreated powder was put into xylene 9 times the weight of the powder and stirred for 1 hour to form a slurry, and the slurry was put in the middle of extrusion using a gear pump, and further extruded. The solvent has been removed by the attached ventro.
  • test piece was cut out from the plate having a thickness of 2 mm and measured using a Tensilon tester in accordance with the method specified in JIS K 7207.
  • a test piece was cut out from the plate having a thickness of 100 ⁇ m, and the oxygen gas permeation rate was measured using an oxygen permeability tester (manufactured by Modern Control Co., Ltd .: OXtran—Twin).
  • a sample of the polyolefin resin composite material of the present invention was prepared using the polyolefin resin and various kinds of treated powders according to the sample preparation method described above, and the physical property evaluation results obtained according to the above evaluation method are shown in Table 2.
  • Table 2 also shows the mixing ratios of the respective materials and the results of evaluating the physical properties of the samples performed in the examples and comparative examples.
  • Comparative Examples 1 and 2 evaluated the physical properties of the samples extruded with the polypropylene resin alone and the polyethylene resin alone.
  • the extruded polypropylene resin had a flexural modulus of 1.37 Gpa and an oxygen permeability of 284 cccm 2 days.
  • Comparative Example 3 when a layered silicate treated organically with only a cationic surfactant was used, the flexural modulus was 1.46 Gpa and the oxygen barrier property was 24. 1 cc / cm 2 / day, which was slightly improved.
  • Example 4 when a layered silicate having a high shape anisotropy effect (swelling my force) is used, the effect of improving the physical properties is further enhanced. Furthermore, as shown in Example 5, it was found that the present invention was effective not only for polypropylene resin but also for other polyolefin resins.
  • Comparative Example 8 uses a method according to the method disclosed in Japanese Patent Application Laid-Open No. Hei 9-138910. This method aims to increase the dispersibility of the crystal flakes by preliminarily impregnating an organic solvent between the layered silicate layers to increase the interlayer distance.
  • an oxygen barrier is used. Although the effect of improving the properties was seen, the flexural modulus was hardly improved because the residual solvent was not easily removed. It is difficult to completely remove the solvent with a ventro of an extruder, which is considered to be an impractical method from an industrial point of view.
  • the montmorite mouth and the swelling force were prepared.
  • compositions were used as the polyolefin resin.
  • peroxides were used for the purpose of causing a graft reaction of unsaturated bonds contained in sodium oleate and acryloyl group-containing sulfonic acid ester to a polypropylene resin.
  • compositions were used as resin oligomers used for comparison with the prior art.
  • Treated Powder G The above 2% aqueous solution of sodium alkylbenzenesulfonate was added dropwise over 3 minutes while stirring 500 g of the DSM denatured swelling my force in a Henschel mixer. After completion of the dropwise addition, stirring was further performed for 10 minutes. The treated powder was held in a vacuum dryer controlled at 70 ° C., and dried for 8 hours to obtain treated powder G.
  • Treated powder H was prepared using sodium oleate in place of sodium alkylbenzenesulfonate in the method of preparing treated powder G above.
  • Processed powder I was prepared by using an atalyloyl group-containing sulfonic ester instead of sodium alkylbenzenesulfonate in the method of preparing the above-mentioned processed powder G.
  • Treated powder J was prepared using ammonium polyphosphate instead of sodium alkylbenzenesulfonate in the method of preparing treated powder G above.
  • Treated Powder K was prepared using a DSDM-modified montmorillon mouth instead of the DSDM-modified swelling force.
  • Treated powder L Among the methods for preparing treated powder G, treated powder L was prepared using a swelling my force that had not been modified with DSDM instead of the DSDM modified swelling force. Untreated fraction: DSDM denatured swelling force was used.
  • Table 3 shows the layered silicates used for the treatment of these treated powders and untreated powders, and their contents.
  • a plate having a thickness of 2 mm or a thickness of 100 ⁇ m was formed in the same manner as in the method of preparing the evaluation sample in the example of the first invention.
  • the mixture was injected at a predetermined mixing ratio in the middle of the extruder using a plunger pump or a gear pump.
  • a plunger pump was used for charging a liquid peroxide (Perhexa 25B) shown in Comparative Example 11 described below.
  • the untreated powder was poured into xylene 9 times the weight of the powder and stirred for 1 hour to prepare a slurry.
  • the slurry was put into the middle of extrusion using a gear pump, and the solvent was removed by a ventro attached to the extruder.
  • a sample of the polyolefin-based resin composite material of the present invention was prepared using the above-mentioned polyolefin-based resin and various kinds of treated powders by the above-described sample preparation method, and the physical properties were evaluated according to the above-described evaluation methods.
  • Table 4 shows the mixing ratio of each material and the results of evaluation of physical properties of the samples performed in the examples and the comparative examples.
  • Comparative Examples 9 and 10 evaluated the properties of samples extruded with the polypropylene resin alone and the polyethylene resin alone.
  • the extruded polypropylene resin had a flexural modulus of 1.37 Gpa and an oxygen permeability of 28.4 cc Zcm 2 days.
  • Comparative Example 13 when a layered silicate organically treated with only a cationic surfactant was used, the flexural modulus was 1.32 Gpa and the oxygen barrier was low. Sex was only slightly improved with SS lcc Z cm 2 days.
  • the polyolefin oligomer having a hydrogen bonding functional group disclosed in Japanese Patent Application Laid-Open No. 10-182892 is used, as shown in Comparative Example 13, the flexural modulus and oxygen barrier properties, and improved 2. 3 2 G pa, 2 6 3 cc / cm 2 days.
  • the flexural modulus is In both cases, a remarkable effect of improving physical properties was observed, with the oxygen barrier property being about 2 times or less that of a single polypropylene and the oxygen barrier property being about 1 Z2 or less of that of a single polypropylene. It should be noted that peroxides were used in Examples 7 and 8, the flexural modulus was 3.22 Gpa and 3.12 Gpa, respectively, and the oxygen permeability was 13 2 cc, respectively.
  • Comparative Example 15 uses the method according to the method disclosed in Japanese Patent Application Laid-Open No. Hei 9-189390. This method aims to increase the dispersibility of the crystal flakes by previously impregnating an organic solvent between the layers of the layered silicate to increase the distance between the layers. Although an improvement effect was observed for, the flexural modulus was hardly improved because the residual solvent was not easily removed. It is difficult to completely remove the solvent at the extruder vent port, which is considered to be an impractical method from an industrial point of view.
  • Plasticizer triethylene glycol-ethylene butyrate 50 parts by weight and organic mesquitite (trade name: SAN, manufactured by Corp Chemical) 7.5 parts by weight with a planetary stirrer for 1 minute A mixture in the form of a gel was obtained.
  • the resulting paste-like mixture 5 7.5 parts by weight of polyvinyl butyral (butyral Ichiru degree 6 5 mole 0/0) 1 0 0 parts by weight Plastograph, 5 at a set temperature 1 4 0 ° C Melted and kneaded for minutes.
  • the completed sample is 200.
  • a sheet having a thickness of 0.5 mm was obtained by a hot press adjusted to a temperature of C.
  • test piece was cut out from the sheet having a thickness of 0.5 mm and measured using a Tensilon tester according to the method specified in JIS K7113.
  • Example 17 B 100 3 GH 50 e 7.5 X 4.0 5.5.6 7.5 54.0 1050
  • A Polyvinyl butyral (.. Butyralization degree 6 5 mole 0 /, polymerization degree 1 7 0 0, residual Asechiru group content 0 5 mole 0/0)
  • the polyolefin-based resin is composed of 100 parts by weight and the organically modified layered silicate in an amount of 0.1 to 50 parts by weight.
  • An organically modified layered silicate obtained by ion-exchanging a metal ion contained as an exchangeable cation with a cationic surfactant.
  • the hydroxyl groups on the crystal side surfaces of the organically modified layered silicate in parentheses are hydroxyl groups. Since it is chemically modified with a chemical substance having a chemical group having a chemical bond or a chemical affinity at the terminal of the molecule, the physical properties such as elastic modulus and gas barrier properties of polyolefin are remarkably improved.
  • the polyolefin-based resin composite material is composed of 100 parts by weight and the organically modified layered silicate in an amount of 0.1 to 50 parts by weight.
  • the organically modified layered silicate obtained by ion-exchange of metal ions contained as exchangeable cations with a cationic surfactant, and the hydroxyl group on the crystal side surface of the organically modified layered silicate is an anionic surfactant.
  • thermoplastic resins because comprising chemically modified by a compound having, in the thermoplastic resin composite material according to c the third invention in which properties such as modulus and Gasubarya of polyolefin fin is significantly improved, thermoplastic resins, layered Since it is a thermoplastic resin composition composed of silicate and a plasticizer, in which the layered silicate is finely dispersed, it has outstanding mechanical strength, high elastic modulus, and reduced bleed-out property of the plasticizer. It is possible to improve. In particular, it is possible to secure a balance between flexibility and strength, which was difficult in the past.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention a trait à un composite de résine polyoléfinique servant de nanocomposite présentant une excellente résistance mécanique, d'excellentes propriétés thermiques et propriétés de barrière au gaz. Le composite contient 100 parties en poids d'une résine polyoléfinique et 0,1 à 50 parties en poids d'un phyllosilicate organisé, le phyllosilicate organisé est du type dans lequel l'ion métal contenu originairement sous la forme de cation échangeable dans la structure de cristal a subi un échange d'ion avec un tensioactif cationique, et dans lequel le groupe hydroxyle présent sur une face latérale du cristal a été modifiée chimiquement à l'aide d'une substance chimique ayant, au niveau d'une extrémité moléculaire, un groupe fonctionnel présentant une capacité de liaison chimique ou une affinité chimique avec le groupe hydroxyle.
PCT/JP2000/002337 1999-04-12 2000-04-10 Composite de resine polyolefinique, composite de resine thermoplastique et procede de production du composite de resine thermoplastique WO2000061676A1 (fr)

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EP00915473A EP1193290A4 (fr) 1999-04-12 2000-04-10 Composite de resine polyolefinique, composite de resine thermoplastique et procede de production du composite de resine thermoplastique

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JP10438099 1999-04-12
JP11/104380 1999-04-12
JP11/203109 1999-07-16
JP11203109A JP2001026724A (ja) 1999-07-16 1999-07-16 熱可塑性樹脂複合材料及びその製造方法
JP11238433A JP2000355640A (ja) 1999-04-12 1999-08-25 ポリオレフィン系複合材料
JP11/238433 1999-08-25
JP11/243800 1999-08-30
JP24380099A JP2001064454A (ja) 1999-08-30 1999-08-30 ポリオレフィン系樹脂複合材料

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Cited By (4)

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WO2002094920A3 (fr) * 2001-05-22 2003-03-27 Dow Chemical Co Nanocomposite de polyolefine modifie de resine hydrogene
WO2004009697A1 (fr) * 2002-07-19 2004-01-29 Asahi Kasei Kabushiki Kaisha Composition de resine polyolefinique
WO2005075569A1 (fr) * 2004-02-04 2005-08-18 Asahi Kasei Life & Living Corporation Matériau composite et matériau composite à base de résine thermoplastique utilisant ce matériau
US12104048B2 (en) 2018-03-29 2024-10-01 Agency For Science, Technology And Research Reinforced polyolefin composite

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BRPI0406799A (pt) 2003-01-15 2006-01-17 Ciba Sc Holding Ag Estabilização de nanocompostos termoplásticos
KR100733922B1 (ko) * 2004-12-03 2007-07-02 주식회사 엘지화학 차단성 물품
DE102005017466A1 (de) * 2005-04-07 2006-10-19 Leibniz-Institut Für Polymerforschung Dresden E.V. Polymerer Nanocomposit und Verfahren zu seiner Herstellung
EP2053020A1 (fr) * 2007-10-22 2009-04-29 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Procédé de préparation d'un matériel cristallin inorganique ayant une structure organisée
EP2407505A1 (fr) * 2010-07-12 2012-01-18 Bayer MaterialScience AG Matériau polymère doté de silicates en couche organiquement modifiés
WO2019083460A1 (fr) * 2017-10-25 2019-05-02 Agency For Science, Technology And Research Émulsion polymère de silicate destinée à un revêtement à barrière élevée

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WO2002094920A3 (fr) * 2001-05-22 2003-03-27 Dow Chemical Co Nanocomposite de polyolefine modifie de resine hydrogene
WO2004009697A1 (fr) * 2002-07-19 2004-01-29 Asahi Kasei Kabushiki Kaisha Composition de resine polyolefinique
CN1307251C (zh) * 2002-07-19 2007-03-28 旭化成株式会社 聚烯烃树脂组合物
WO2005075569A1 (fr) * 2004-02-04 2005-08-18 Asahi Kasei Life & Living Corporation Matériau composite et matériau composite à base de résine thermoplastique utilisant ce matériau
US12104048B2 (en) 2018-03-29 2024-10-01 Agency For Science, Technology And Research Reinforced polyolefin composite

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